JPS6019766B2 - How to polymerize olefins - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for polymerizing olefins using a novel catalyst. More specifically, the present invention uses a novel catalyst comprising a combination of a special organomagnesium compound, a specific aluminum compound, a titanium compound, and/or a vanadium compound and an organoaluminium compound to react with ethylene or ethylene and other Q-olefins. The present invention relates to a method for producing a polyolefin with excellent moldability by polymerization using a solution polymerization method. For example, solution polymerization is already known as a suitable method for producing polyethylene. The advantages of this solution polymerization include the following. '
1} Ethylene polymerization is an exothermic reaction, and heat removal is a major problem in the process, but solution polymerization has a high reaction temperature, so there is a large temperature difference between the inner stripe and the jacket, so heat removal efficiency is good. This becomes more advantageous as the polymerization temperature becomes higher. {The degree of polymerization of 2' ethylene, that is, the molecular weight of polyethylene, can be controlled relatively accurately by changing the reaction temperature, and molecular weight control can be achieved by using a small amount of hydrogen. {3) Since there is a correlation between the molecular weight of polyethylene and the viscosity of the reaction solution, it is possible to estimate the molecular weight of polyethylene and take prompt action by measuring the viscosity of the solution inside the reactor. {4- Polyethylene is generally used in the form of pellets, and polyethylene produced by suspension polymerization or gas phase polymerization is in the form of powder, and extra energy is required to form it into pellets using an extruder. In solution polymerization, the heat of polymerization is used to evaporate the solvent and at the same time introduce molten polyethylene into an extruder, which is extremely advantageous in terms of effective use of energy. To take advantage of this advantage, higher polymerization temperatures are desirable. On the other hand, the problem with solution polymerization is that when the concentration of the solution is increased or the molecular weight of polyethylene is increased, the viscosity of the solution increases.
This makes implementation on a factory scale difficult. To solve this problem, it is necessary to raise the polymerization temperature and lower the solution viscosity. However, when the polymerization temperature is raised, the catalyst efficiency decreases and a large amount of catalyst residue remains in the polyethylene. As a result, the polyethylene becomes colored and the product deteriorates after molding, and it is difficult to remove the remaining dissolved catalyst. Therefore, there is little catalyst residue in polyethylene,
Catalysts with high catalytic efficiency at high temperatures such that a removal step is not required are needed. In the suspension polymerization method, many Ziegler type catalysts with high catalytic efficiency are known. However, the catalyst efficiency of these catalysts generally decreases when the polymerization temperature is increased, and the decrease is particularly significant at temperatures above 15,000, and the performance is insufficient for omitting the catalyst residue removal step in solution polymerization. On the other hand, catalysts for solution polymerization of olefins using organomagnesium complexes, halides, and titanium compounds have been disclosed (Japanese Patent Publication No. 47-1372, JP-A-5
No. 0-143883, Special Seki No. 51-144397). Although these catalysts have higher catalytic efficiency than conventional catalysts, their catalytic efficiency is still insufficient, especially at high temperatures. The present inventors investigated solution polymerization catalysts and found that an organoaluminum compound was combined with a catalyst component made by contacting a titanium compound and/or a vanadium compound with a reaction product of a special organomagnesium compound and a specific aluminum compound. As a result, they found a catalyst that has extremely high catalytic efficiency, exhibits little drop in catalytic efficiency even at temperatures of 120° C. or higher, especially 15,000° C. or higher, is stable and can be stored for a long period of time, and has developed the present invention. That is, the present invention provides (i) the general formula MQ MgR1pR2qX1rX2S, where M is a metal atom of Group 1 to Group m of the periodic table, Q is a rainbow, q, r, and s are numbers greater than or equal to 0, and p+q+r+s =mQ+2, 0<(r1s)/
(Q+1)≦1.5, m is the valence of M, R
1, R2 has 1 to 20 carbon atoms, which may be the same or different
a hydrocarbon group, X, X2 are the same or different groups and represent a hydrogen atom or a negative group containing an oxygen, nitrogen or sulfur atom) and an organic magnesium compound soluble in a hydrocarbon solvent; ii) General formula AIX3x
Yy (wherein X3 is alkoxy, siloxy, allyloxy,
Amino, amide, imide, alkylthio group, Y is a halogen atom, x, y are 0<x<3, 0<y<3, x+
A catalyst component formed by contacting (iii) a titanium compound and/or a vanadium compound with a reactant of an aluminum compound represented by y=3 (representing a number having the relationship y=3)
A] and organoaluminum compound [B], 12
The present invention relates to an olefin polymerization method in which olefin alone, ethylene and Q-olefin other than ethylene or diolefin are polymerized in a solution state in one stage or in multiple stages at a temperature of 0 qo or higher. The features of the present invention will be explained below. The first feature of the present invention is high catalyst efficiency. As is clear from the examples described later, the catalyst efficiency is 200k.
9/tanj+V)・Hr or more can be achieved,
This makes it possible to omit the catalyst residue removal step. The second feature of the present invention is that it is stable even at high temperatures. As is clear from the examples described below, a catalyst efficiency of 200 kg/tanj+V)·Hr can be achieved even at 150 oo or more. A third feature of the present invention is that it provides a high molecular weight, high stiffness polymer that has a narrow molecular weight distribution and can be passed through injection molding. As shown in the Examples below, it is possible to produce a polymer with an extremely narrow molecular weight distribution of FR20 or less. The fourth feature of the present invention is that polymers with a wide molecular weight distribution and suitable for extrusion molding can be produced by performing polymerization using a multistage reaction zone in which conditions such as the temperature and hydrogen concentration of the reaction zone are changed. be. The general formula MQMgR1pR2qX1rX2s used in the catalyst of the present invention (in the formula M, R1,
The organomagnesium compound (i) (R2, X1, X2, Q, p, q, r, s have the above-mentioned meanings) will be explained. Although (i) is shown as an organomagnesium compound, it includes all dialkylmagnesiums and their combinations with other metal compounds. In the above formula, M can be a metal element belonging to Group 1 to Group M of the periodic table, such as lithium, sodium, potassium,
Beryllium, calcium, strontium, barium,
Examples include zinc, boron, aluminum, etc., and lithium, beryllium, boron, aluminum, and zinc are particularly preferred because they facilitate the production of organomagnesium compounds that are soluble in hydrocarbon solvents. Furthermore, aluminum is preferably used. The ratio Q of metal atoms M to magnesium atoms is Q=
Although it can be set arbitrarily including the dialkylmagnesium conductor which is 0, it is preferable to use OSQS1, especially OSQ
S.O. Organomagnesium rust bodies soluble in hydrocarbon solvents as shown in No. 5 are preferred. The hydrocarbon group represented by RI to R2 is a hard alkyl group, cycloalkyl group or allyl group having 1 to 2 carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, Examples include phenyl and benzyl groups, with alkyl groups being particularly preferred. On the other hand, when Q=0, in order to obtain an organomagnesium compound soluble in a hydrocarbon solvent, R1, R
2 hydrocarbon groups are limited. For example, the first case is when RI and/or R2 are secondary or tertiary alkyl groups having 3 or more carbon atoms. The second is that RI has 2 to 6 carbon atoms.
The alkyl group R2 is an alkyl group having 4 or more carbon atoms, and the difference in the number of carbon atoms between RI and R2 is 2 or more. Specifically, (sec-C4 ratio) 2M
g, (sec-C44) Mg (n-C4 day 9), (is
o-C3 day 7) Mg (n-C4 day 9), (C2 public) Mg
(n-C4 ratio) etc. are used. Further, in order to reduce the viscosity of the R2Mg solution, it is advantageous to add a small amount of an organic metal. X1 and X2 are hydrogen atoms or oxygen,
It represents a negative group containing a nitrogen or sulfur atom, preferably alkoxy, siloxy, allyloxy, amino, amido, imide, alkylthio, or 8-keto acid residue, and more preferably an alkoxy group or siloxy group. Relational expression of symbols Q, p, q, r, s p 1 q + r + s = mQ
+2 indicates the stoichiometry between the valence of the metal atom and the substituent, and is in a preferred range of 0<(r1s)/(Q+1)S
I. 5 indicates that the sum of XI and X2 is greater than 0 and 1.5 or less with respect to the sum of metal atoms. In order to increase the stability of the catalyst component [A] and increase the catalyst efficiency at high temperatures, containing XI or X2 as a substituent,
In other words, (r+s)>0 is required. Preferably 0.
2≦(r+s)/(Q+1)SI. 3 Particularly preferably,
The range is 0.3≦(r10s)/(Q+1)≦1.0. These organomagnesium compounds have the general formula RIMg
A compound represented by Q, R Mine Mg (RI has the above-mentioned meaning, Q is a halogen atom), and a compound represented by the general formula M liver 2m, M
R is also X1bX2c, MQX1bX2c, (M, R2,
1, X2, Q, m have the above meanings, a, b, c are a
+b+c=m) in an inert hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, etc.
and, if necessary, further reacting these with an alcohol, siloxane, amine, imine, thiol, or dithio compound. Furthermore, organomagnesium compounds include MgX chamber, RIMg
XI and MR, MR2m-, day, or RIMgX1,
R Mg and R2J × 2m-n or RIMg
X1, R ki Mg and XlamX2 Sena (in the formula M, R1,
R2, X1, X2, m have the above-mentioned meanings, and X1, X2
is a halogen, a is a number from 0 to m)
It can be synthesized by reaction with Next, the general formula NX3xYy (
In the formula, X3, Y, x, y have the above-mentioned meanings) An aluminum compound (ii) will be explained.
An alkoxy group or a siloxy group is used. Y is
A fluorine, chlorine, bromine or iodine atom, with a chlorine atom being recommended. Symbols x and y are 0<xku3, 0<y<
3, which is a number having the relationship x+y=3. component (l) and

In order to efficiently react [ii] and produce a catalyst that gives a polymer with a narrow molecular weight distribution, x must be
It is important that xS2 be in the range and that (ii) is soluble in the hydrocarbon solvent. Specifically, these compounds are C3 day 70 mountain CI2, C4 day 90 AIC12,
C5th day. 〇AIC12, C6 days, 30AIC12, C
7th, 50MCI2, C8th, 70AIC12, C9H
I9MCI2 ・CI. H illusion. Rainbow CI2 ・C6 day 50
AIC12 ・C6th,. OAIC12, (C
4 ratio○)2AIC1(C5day,.○)2MCI
, (C6 day, 30)2AIC1, (C7 day, 5
0) 2 mountains CI, (C8th, 70) 2AIC1
,(C9day,90)2AIC1,(C,.day2,
0)2NC1, (C&)3SjOAIC12, Japan/
CH3・C2日5SiOAIC12、日・(CH3
)2SiOAIC12, (Japanese/CH3/C2 expanded Si
○) 2AIC1, C4th 9SNC12, C6th, 3SA
IC12, C, Pan2, SNC12, (CH3)2NNC
12, etc. alone and mixtures thereof. Examples of the titanium compound and/or vanadium compound include titanium tetrachloride, titanium tetrabromide, titanium tetrachloride, ethoxytitanium trichloride, proboxytitanium trichloride,
Butoxytitanium trichloride, diproboxytitanium dichloride, dibutoxytitanium dichloride, tribropoxytitanium chloride, tributoxytitanium chloride, tetraproboxytitanium, tetrabutoxytitanium, vanadium tetrachloride, vanadyl trichloride, butoxyvanadyl dichloride, dibutoxy Titanium and vanadium halides, oxyhalides, alkoxyhalides, alkoxide compounds, and oxyalkoxide compounds such as vanadyl chloride and tributoxyvanadyl may be used alone or in mixtures. To achieve highly active catalytic performance, titanium compounds containing at least one chlorine atom, preferably at least three chlorine atoms, or
Preference is given to using vanadium compounds and titanium compounds containing at least three halogen atoms. Components 'i) and (ii), the kite reaction is carried out using inert reaction solvents, such as aliphatic hydrocarbons such as hexane, heptane, octane, hydrogen aromatics such as benzene, toluene, and fats such as cyclohexane, methylcyclohexane. The reaction can be carried out in a cyclic hydrocarbon or a mixture thereof. From the viewpoint of catalyst performance, an aliphatic hydrocarbon solvent is preferably used. [The reaction order of (i), [ii), and (iii)] However, in order to exhibit highly active catalytic performance, it is necessary to avoid contact between (i) and (ii) in advance. components and effectively (
By contacting ili), the surprising effects of the present invention are achieved. The reactions (i) and (ii) are carried out by a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted;
Alternatively, one type of component is charged into the reaction zone in advance, and then the remaining one type of component is introduced and reacted, so-called forward (reverse).
Any method of addition is possible. There is no particular restriction on the reaction temperature, but from the viewpoint of reaction progress it is preferably -
5000-15000, particularly preferably 2000-10
Implemented at 00C. There is no particular restriction on the reaction ratio of the two components, but preferably (1 mol of component (i))
The recommended amount of component ii) is 0.01 to 10 mol, particularly preferably 0.1 mol to 2 mol. A solid component is produced by the reaction of (i) and (ii), but
This can be isolated by filtration, etc., or washed by decantation, and then reacted with the seeds, but in order to simplify the reaction operation, after the completion of the reactions (i) and (ii),
It is preferable to introduce a kite into this reaction solution to further advance the reaction. (iii) should be used in a molar ratio of 3≦Mg/(Ti
+V) S500, preferably 5≦Mg/(Ti+V)≦
200 Particularly preferably 10≦Mg(Ti+V)SIOO
The concentration of Ti+V in the reaction solution was 2 mol.
It is preferable to do it below . There is no particular restriction on the reaction temperature, but it is preferably 150 qo to 150 qo from the viewpoint of reaction progress.
0, preferably in the range of 000 to 95 qo.
Although the catalyst component [A] of the present invention is useful as a catalyst for ethylene polymerization as it is, it becomes an even more excellent catalyst when combined with an organoaluminum compound. As the organic aluminum compound [B], AI(C2day5)3
, Mountain (C3 day 7) 3, AI (C4 day 9) 3, AI (C5 day 9)
Day,. ) 3, AI (C6th, 3) 3, Mountain (C8th, 7)
3, AI (C, Rainbow 2,) 3 grade trialkyl aluminum, isoprenyl aluminum, N (C2 days 5) 2 days,
Mountain (i-C4) 2nd etc. alkyl aluminum hydride, N. (C2 day 5) 2CI, mountain (C2 public) CI2
, N(i-C4) CI2, Alkylaluminium halide such as AI(C2day5)2Br, N(C2day5)2
Alkoxyalkyl aluminum such as (OC2 public), Yama (i-C4 ratio) 2 (OC4 day 9), AI (C2 day 5) 2
・(OSiHCH3C 2 days 5), AI (i-C 4 days 9)
Siloxyalkylaluminums such as 2.2 (OSi(CH3)2i-C4day9) and mixtures thereof are used. In order to achieve high activity, the use of trialkylaluminum is preferred. Catalyst components [A] and [B] may be added into the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. The ratio of both components to be combined is defined by the molar ratio of Ti+V in the [A] component and AI in the [B] component, and is preferably AI/(T
i+V) is 3/1 to 1000/1, more preferably 5
A range of /1 to 500/1 is used. The catalyst of the present invention is suitable for the polymerization of ethylene, but also for the polymerization of Q-olefins or diolefins such as propylene, butene-1, isoptene, hexene-1, 4-methylbentene-1, octene-1, decene-1, butadiene, isoprene, etc. It is also possible to perform copolymerization with ethylene in the coexistence, and it is particularly preferable to use 5 hol or less of Q-olefin having 3 to 20 carbon atoms per 1 mol of ethylene. Density 0.975-0.9 by homopolymerization and copolymerization
It is possible to produce a range of 10 polyethylenes. Polymerization is higher than 120qo, preferably higher than 150qo and 320qo
It is carried out by solution polymerization methods in the temperature range up to °C. As the polymerization solvent, aliphatic hydrocarbons such as hexane, hebutane, and octane, aromatic hydrocarbons such as benzene, toluene/xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are used. The catalyst is introduced into the reactor together with the polymerization solvent, and ethylene is heated at 0.1 Mma to 4 MPa, preferably IMPa to 2 MPa under an inert atmosphere.
Polymerization can be carried out by introducing the ethylene at a partial pressure of 8 MPa and mixing with a strainer to ensure good contact between ethylene and the catalyst. The polymerization may be carried out in a single-stage polymerization using one reaction zone, or it is also possible to carry out a so-called multi-stage polymerization using a plurality of reaction zones. Although this catalyst yields polyethylene with a narrow molecular weight distribution in one stage polymerization, it is also possible to produce polyethylene with a wide molecular weight distribution through multistage polymerization. Furthermore, in order to control the molecular weight, it is also possible to change the temperature of the reactor or add hydrogen or an organic compound that is likely to cause chain transfer. Furthermore, it is also possible to carry out the polymerization by combining methods such as adding a titanate ester to adjust the density. Examples of the present invention are shown below, but the present invention is not limited to these examples in any way. In addition, in these examples, MI represents melt index, and the temperature is 190qC according to ASTM D-1238.
, measured under a load of 2.16 kg. F
R means the quotient obtained by dividing the value measured at a temperature of 190q0 and a load of 21.6[9] by MI, and is one of the measures of molecular weight distribution, and the lower the value, the narrower the molecular weight distribution. Catalyst efficiency is (Ti + V) polymer production amount k per night/hour
It is represented by 9. Example 1 [1] Synthesis of hydrocarbon solvent soluble organomagnesium compound (i) Nitrogen-substituted 2
500g of magnesium powder was added to a 000ml flask. Of the mixture of 20.8 parts n-butyl chloride and 60 parts n-octane, 20 volumes were introduced into the flask. The flask was heated and heated under reflux. After the reaction started, the remaining n-butyl chloride was added dropwise under reflux for 2 hours, and after the reaction was completed, the mixture was heated for another 1 hour. In addition to this, AIC12 (
0 m-C3 days 7) n-octane containing 35 mmol 20
An organomagnesium compound solution was obtained by adding and reacting for 70,002 hours. As a result of analysis, the composition of this collar body was found to be AIo. 5Mg(n-C4)2.9(0n-
C3 day 7) o. 5, and the organometallic concentration is 1. enemy hol
'It was sleeved. AIC12 (0m-C3 days 7) was synthesized by reacting aluminum powder, AIC13, and n-C3H70H in n-octane at a molar ratio of 1:2:3.

[0] Synthesis of catalyst component [A] Oxygen and moisture inside a 250-ml flask equipped with a dropping funnel and a water-cooled reflux condenser were removed by nitrogen substitution, and 0.2 mol of dichlorobutoxyaluminum was added under a nitrogen atmosphere. 24 of the n-octane solution and 30 of the n-octane solution were charged and the temperature was raised to 7,000 ℃. Next, 4.0' of component (i) and 20' of n-octane were weighed into the dropping funnel. At 70:00, it was dripped under the fly Azusa over a period of 2 hours. The reaction solution became a white suspension. This white suspension contained 22 n-octane containing 0.16 mmol of titanium tetrachloride.
was introduced, and the reaction was carried out at 70 qo for 1 hour. [m]
Polymerization of ethylene

Catalyst component [A] synthesized in [0] 3.0
0.144 mmol of trioctylaluminum and 0.6 mmol of dehydrated and degassed n-octane were placed in an autoclave whose interior was vacuum degassed. Next, after charging 50 mmol of hydrogen, the autoclave was kept at 160 oo, ethylene was pressurized at a pressure of 4.0 MPa, and polymerization was carried out for 4 minutes while keeping the total pressure constant by replenishing ethylene. As a result, a polymer having a weight of 81 mm was obtained. Catalyst efficiency is 527kg/〇i+V)
Hr and MI were 2.6, FR was 18, and density was 0.969. Examples 2 to 12 Catalyst component [A] was synthesized according to the method of Example 1 using components (i), (ii), (iiD) and reaction conditions shown in Table 1. Catalyst component [A] Polymerization was carried out in the same manner as in Example 1, except for the organoaluminum compound [B] and polymerization conditions shown in Table 3. Table U Example 13 Catalyst component synthesized in Example 1 [A] Using 0.04 mmol of ethyl aluminum and 1.2 mol of ethylene according to the method of Example 1 under the conditions of ethylene pressure 2.0 MPa, hydrogen 2 mmol, and polymerization temperature 140 qo.
Polymerization was carried out. Next, 200 mmol of hydrogen was introduced and the temperature was lowered to 180 qo.
After raising the temperature to 2.2, the ethylene partial pressure was increased again. Ethylene 1. Polymerization of adhol was carried out. As a result, M
IO. A polymer with a gunwale of FR96 was obtained. Example 14-1
9AI〇,33Mg (n-C4 days 9) 2 (〇n-C6 days 13) 2 units mol, n-C4 days 90AIC121.5m
Catalyst component [A] was synthesized in the same manner as in Example 1 except that mol and TIC were used in an amount of 140.10 mmol. This was introduced into an autoclave whose interior was vacuum degassed, along with 0.6 hexane from which 30.08 mmol of AI (C2 day 5) had been dehydrated and degassed. Next, after adding 16 mol of hydrogen and the olefin shown in Table m, 155 q
Raise the temperature to o. Ethylene was pressurized to a partial pressure of 3.0 MPa, and polymerization was carried out for 3 minutes while maintaining the total pressure by replenishing ethylene, and the results shown in Table m were obtained. Town table

Claims (1)

[Claims] 1 (i) General formula MαMgR^1_pR^2_qX^
1 _ r
r+s=mα+2, 0<(r+s)/(α+1)≦1.
5, where m is the valence of M, R^1 and R^2 are hydrocarbon groups having 1 to 20 carbon atoms which may be the same or different, and X^1 and X^2 are the same or different. and (ii) an organomagnesium compound soluble in a hydrocarbon solvent represented by a hydrogen atom or a negative group containing an oxygen, nitrogen or sulfur atom;
In the formula, X^3 represents an alkoxy, siloxy, allyloxy, amino, amide, imide, or alkylthio group, Y is a halogen atom, and x and y are 0<x<3, 0<y<3, x+y
(representing a number having a relationship of =3), (iii) a titanium compound and/or
Or a catalyst component made by contacting a vanadium compound [A
] and organoaluminum compound [B], 120
A method for polymerizing olefins, in which olefin alone, ethylene and α-olefin other than ethylene or diolefin are polymerized in a solution state in one stage or in multiple stages at a temperature of 0.degree. C. or higher. 2 General formula MαMgR^1_pR^2_qX^1_rX
2. The method for polymerizing an olefin according to claim 1, wherein M is a lithium, beryllium, boron, aluminum, or zinc atom in the organomagnesium compound which is ^2_s. 3 General formula MαMgR^1_pR^2_qX^1_rX
2. The method for polymerizing an olefin according to claim 1 or 2, wherein M in the organomagnesium compound ^2_s is an aluminum atom. 4 General formula MαMgR^1_pR^2_qX^1_rX
α of the organomagnesium compound that is ^2_s is 0≦α≦
1. A method for polymerizing an olefin according to any one of claims 1, 2, and 3. 5 General formula MαMgR^1_pR^2_qX^1_rX
α of the organomagnesium compound that is ^2_s is 0≦α≦
0.5. A method for polymerizing an olefin according to any one of claims 1, 2, 3, or 4. 6 General formula MαMgR^1_pR^2_qX^1_rX
Claims 1 and 2, wherein X^1 or X^2 of the organomagnesium compound that is ^2_s is an alkoxy, siloxy, allyloxy, amino, amide, imide, alkylthio, β-keto acid residue, A method for polymerizing an olefin according to any one of Item 3, Item 4, and Item 5. 7 General formula MαMgR^1_pR^2_qX^1_rX
Claims 1, 2, 3, 4, 5, or 6, wherein X^1 or X^2 of the organomagnesium compound that is ^2_s is an alkoxy group or a siloxy group. A method for polymerizing an olefin according to any one of the above. 8 General formula MαMgR^1_pR^2_qX^1_rX
In the organomagnesium compound which is ^2_s, 0.
2≦(r+s)/(α+1)≦1.3 in any of claims 1, 2, 3, 4, 5, 6, or 7. A method of polymerizing the described olefins. 9 General formula MαMgR^1_pR^2_qX^1_rX
In the organomagnesium compound which is ^2_s, 0.
3≦(r+s)/(α+1)≦1.0 Claims 1, 2, 3, 4, 5, 6, 7, or 8 A method for polymerizing an olefin according to any one of the above. 10. The method for polymerizing an olefin according to claim 1, wherein X^3 of the aluminum compound having the general formula AlX^3_xY_y is an alkoxy group or a siloxy group. 11. The method for polymerizing an olefin according to claim 1 or 10, wherein Y in the aluminum compound having the general formula AlX^3_xY_y is a chlorine atom. 12 The aluminum compound according to claim 1, 10 or 11, wherein x of the aluminum compound having the general formula AlX^3_xY_y satisfies 1≦x≦2 and is soluble in a hydrocarbon solvent. A method of polymerizing olefins. 13. The method for polymerizing olefins according to claim 1, wherein the titanium compound in (iii) is a titanium compound containing at least one chlorine atom. 14. A method for polymerizing olefins according to claim 1 or 13, wherein the titanium compound in (iii) is a titanium compound containing at least 3 chlorine atoms. 15. A method for polymerizing an olefin according to claim 1, wherein (iii) is a vanadium compound and a titanium compound containing at least three chlorine atoms. 16. The method for polymerizing olefins according to claim 1, wherein the reaction of (i) and (ii) is carried out at a temperature of -50°C to 150°C. 17 The molar ratio of (i) and (ii) is 1:0.01 to 1:10
17. The method for polymerizing olefins according to claim 1 or 16, characterized in that the reaction is carried out in a range of 0. 18 Claim 1, characterized in that the reaction is carried out at a molar ratio of (i) and (ii) in the range of 1:0.1 to 1:20.
A method for polymerizing an olefin according to any one of Items 16 and 17. 19. The method for polymerizing olefins according to claim 1, characterized in that the contacting of (iii) with the reactants of (i) and (ii) is carried out at a temperature of -50°C to 150°C. 20. Claims 1 or 19, characterized in that when (iii) is brought into contact with the reactants of (i) and (ii), the temperature is from 0°C to 95°C. A method of polymerizing olefins. 21. Any one of Claims 1, 19, or 20, in which (iii) is brought into contact with the reactants of (i) and (ii), and Mg/(Ti+V) is in the range of 3 to 500. A method for polymerizing olefins as described in . 22 When (iii) is brought into contact with the reactants of (i) and (ii), Mg/(Ti+V) is in the range of 5 to 200. 21
A method of polymerizing an olefin according to any of the above. 23 When (iii) is brought into contact with the reactants of (i) and (ii), Mg/(Ti+V) is carried out in the range of 10 to 100. A method for polymerizing an olefin according to any one of Item 21 and Item 22. 24 When (iii) is brought into contact with the reactants of (i) and (ii), the concentration of Ti+V is 2 mol/l or less.Claims 1, 19, 20, and 21 A method for polymerizing an olefin according to any one of Items 22 and 23. 25. The method for polymerizing olefins according to claim 1, wherein the organomagnesium compound [B] is trialkylaluminum. 26 The molar ratio of Ti+V in [A] and [B] is Al/(
26. The method for polymerizing olefins according to claim 1 or 25, characterized in that Ti+V) is used in the range of 3/1 to 1000/1. 27. The method for polymerizing olefins according to claim 1, wherein the polymerization of ethylene is carried out under conditions of 150°C to 320°C and an ethylene partial pressure of 1.0 to 25 megapascals (MPa). 28. A method for polymerizing olefins according to claim 1, characterized in that [A] and [B] are used to copolymerize ethylene and an α-olefin or diolefin other than ethylene. 29 In claim 28, the number of carbon atoms is 3
~20 α-olefins per mol of ethylene
A method for polymerizing olefins used under conditions of mol or less.